Solution-processed Poly Research Articles

Tunable hole injection of solution-processed polymeric carbon nitride towards efficient organic light-emitting diode

Polymeric carbon nitride (CNxHy) has been facilely synthesized from dicyandiamide and functions as a solution-processed hole injection layer in organic light-emitting diodes (OLEDs). The measurements using X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and impedance spectroscopy elucidate that CNxHy exhibits superior film morphology and extra electric properties such as tailored work function and tunable hole injection. The luminous efficiency of CNxHy-based OLED is found to improve by 76.6% in comparison to the counterpart using favorite solution-processed poly(ethylene dioxythiophene):poly(styrene sulfonate) as the hole injection layer. Our results also pave a way for broadening carbon nitride applications in organic electronics using the solution process.

Self-assembled H-aggregation induced high performance poly (3-hexylthiophene) Schottky diode

The investigation of size confinement and chain orientation within the microstructure of a polymer thin film is very important for electronic device applications and fundamental research. Here, we present single step methodology for the synthesis of solution-processable poly (3-hexylthiophene) (P3HT) nanofibers via a self-assembly process. The formation of P3HT nanofibers is confirmed by atomic force microscopy. The synthesized nanofibers are characterized by UV-visible absorption, photoluminescence, and Raman spectroscopy. The aggregation type of self-assembled P3HT is studied by both UV-visible absorbance and photoluminescence spectroscopy. The exciton bandwidth in polymer films is calculated by following the Spano's H-aggregate model and found to be 28 meV. Raman spectroscopy is used to identify the various stretching modes present in nanofibers. The structural investigation using grazing angle X-ray diffraction of nanofibers reveals the presence of alkyl chain ordering. We have fabricated organic Schottky diodes with P3HT nanofibers on indium tin oxide (ITO) coated glass with configuration Al/P3HT/ITO, and current density-voltage characteristics are subsequently used for extracting the electronic parameters of the device. We have also discussed the charge transport mechanism at the metal/polymer interface.

High-Performance Polymer Solar Cells Employing Rhodamines as Cathode Interfacial Layers.

The development of simple and water-/alcohol-soluble interfacial materials is crucial for the cost-effective fabrication process of polymer solar cells (PSCs). Herein, highly efficient PSCs are reported employing water-/alcohol-soluble and low-cost rhodamines as cathode interfacial layers (CILs). The results reveal that rhodamine-based CILs can reduce the work function of the Al cathode and simultaneously increase the open-circuit voltage, current density, fill factor, and power conversion efficiency (PCE) of PSCs. The solution-processed rhodamine-based PSCs demonstrated a remarkable PCE of 10.39%, which is one of the best efficiencies reported for thieno[3,4-b]thiophene/benzodithiophene:[6,6]-phenyl C71-butyric acid methyl ester-based PSCs so far. The efficiency is also 42.3% higher than that of the vacuum-deposited Ca-based device (PCE of 7.30%) and 21.5% higher than that of the complicated solution-processable polymeric electrolyte poly[(9,9-bis(3-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]-based device (PCE of 8.55%). Notably, rhodamines are very economical and have been extensively used as dyes in industries. Our work indicates that rhodamines have shown a strong potential as CILs compared to their counterparts in the large-area fabrication process of PSCs.

Investigation of the optical and electrical characteristics of solution-processed poly (3 hexylthiophene) (P3HT): multiwall carbon nanotube (MWCNT) composite-based devices

Devices comprised of solution-processed poly (3-hexylthiophene) (P3HT)/multiwall carbon nanotubes (MWCNTs), with various concentrations of MWCNTs, were fabricated and characterized. The morphology of the P3HT: MWCNT nanocomposite was characterized by using field emission scanning electron microscopy (FESEM). The optical characteristics of the nanocomposite were studied by UV/VIS/NIR spectroscopy and Raman spectroscopy. The electrical properties of the fabricated devices were characterized by measuring the current density–voltage (J–V) characteristics. While the J–V characteristics of a pristine P3HT device reveal thermal injection limited charge transport, the P3HT: MWCNT nanocomposite-based devices exhibit three distinct voltage-dependent conduction regimes. The fitting curve with measured data reveals Ohmic conduction for a low voltage range, a trap-charge limited conduction (TCLC) process at an intermediate voltage range followed by a trap free space-charge limited conduction (SCLC) process at much higher voltages. A fundamental understanding of this work can assist in creating new charge transport pathways which will provide new avenues for the development of highly efficient polymer-based optoelectronic devices.

Inverse Magnetoresistance in Polymer Spin Valves.

In this work, both negative and positive magnetoresistance (MR) in solution-processed regioregular poly(3-hexylthiophene) (RR-P3HT) is observed in organic spin valves (OSVs) with vertical La2/3Sr1/3MnO3 (LSMO)/P3HT/AlOx/Co configuration. The ferromagnetic (FM) LSMO electrode with near-atomic flatness is fabricated by a DC facing-target magnetron sputtering method. This research is focused on the origin of the MR inversion. Two types of devices are investigated in details: One with Co penetration shows a negative MR of 0.2%, while the other well-defined device with a nonlinear behavior has a positive MR of 15.6%. The MR measurements in LSMO/AlOx/Co and LSMO/Co junctions are carried to exclude the interference of insulating layer and two FM electrodes themselves. By examining the Co thicknesses and their corresponding magnetic hysteresis loops, a spin-dependent hybrid-interface-state model by Co penetration is induced to explain the MR sign inversion. These results proven by density functional theory (DFT) calculations may shed light on the controllable interfacial properties in designing novel OSV devices.

Influence of the Hole Transporting Layer on the Thermal Stability of Inverted Organic Photovoltaics Using Accelerated-Heat Lifetime Protocols.

High power conversion efficiency (PCE) inverted organic photovoltaics (OPVs) usually use thermally evaporated MoO3 as a hole transporting layer (HTL). Despite the high PCE values reported, stability investigations are still limited and the exact degradation mechanisms of inverted OPVs using thermally evaporated MoO3 HTL remain unclear under different environmental stress factors. In this study, we monitor the accelerated lifetime performance under the ISOS-D-2 protocol (heat conditions 65 °C) of nonencapsulated inverted OPVs based on the thiophene-based active layer materials poly(3-hexylthiophene) (P3HT), poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7), and thieno[3,2-b]thiophene-diketopyrrolopyrrole (DPPTTT) blended with [6,6]-phenyl C71-butyric acid methyl ester (PC[70]BM). The presented investigation of degradation mechanisms focus on optimized P3HT:PC[70]BM-based inverted OPVs. Specifically, we present a systematic study on the thermal stability of inverted P3HT:PC[70]BM OPVs using solution-processed poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) and evaporated MoO3 HTL. Using a series of measurements and reverse engineering methods, we report that the P3HT:PC[70]BM/MoO3 interface is the main origin of failure of the P3HT:PC[70]BM-based inverted OPVs under intense heat conditions, a trend that is also observed for the other two thiophene-based polymers used in this study.

Effects of silicon Interface and frequency dependence in solution-processed high-K poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) dielectric characteristics

A solution-based ferroelectric relaxor poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) terpolymer, P(VDF–TrFE–CTFE), is employed in a metal-insulator-semiconductor (MIS) capacitor as a high-k dielectric material. Based on experimental characterizations, the capacitance of the MIS structure is decreased with P(VDF-TrFE-CTFE) thickness reduced. Examined by electrical characterizations, an equivalent interface layer at the P(VDF-TrFE-CTFE)/silicon interface is proposed in this work. This shows that the P(VDF–TrFE–CTFE) film thickness is an important factor while using it as a high-k dielectric material in devices. At the same time, experimental results also show a low remnant polarization and low coercive field of 1.23μC/cm2 and 0.176MV/cm, respectively. This indicates operating frequency is also a factor of its effective dielectric constant. In our experimental results, the maximum dielectric constant is 32.4 at 1kHz with 2900nm film thickness. For applications in different organic electronics, therefore, this study demonstrates that P(VDF–TrFE–CTFE) is a frequency/thickness dependent high-k dielectric material.

Low-Molecular-Weight, High-Mechanical-Strength, and Solution-Processable Telechelic Poly(ether imide) End-Capped with Ureidopyrimidinone

Solution-processable poly(ether imide)s (PEIs) with ureidopyrimidinone (UPy) end groups were prepared by incorporating monoisocyanato-6-methylisocytosine into amine-terminated PEI oligomers. After functionalization with UPy end groups, PEI with a molecular weight as low as 8 kDa (8k-PEI-UPy) can be solution-cast to form films. Tensile tests revealed that 8k-PEI-UPy had an outstanding Young’s modulus higher than those of state-of-the-art high-molecular-weight commercial PEIs. The tensile strength, maximum elongation, and Young’s modulus of 8k-PEI-UPy were 87.2 ± 10.8 MPa, 3.10 ± 0.39%, and (3.20 ± 0.14) × 103 MPa, respectively. The discovery herein significantly advances the chemistry of high-temperature PEI resins. UPy-based supramolecular chemistry is an effective and general strategy to achieve outstanding mechanical properties for PEI oligomers.

A new biodegradable gate dielectric material based on keratin protein for organic thin film transistors

By virtue of the biocompatibility, environmental benignity, and sustainability, as well as low cost of keratin protein's source herein, we report its application as a gate dielectric material for organic electronic devices. Keratin protein, which is a biodegradable material was directly extracted from poultry chicken feathers (CFs). Solution-processed regioregular poly(3-hexylthiophene) (P3HT) organic thin film transistors (OTFTs) with keratin dielectric thin film exhibited enhanced charge mobility of 2.293 × 10−3 cm2 V−1 s−1 (saturation regime), high on-off current ratio of 105 and low threshold voltage, -1V as compared to conventional SiO2 dielectric. All the fabrication processes were performed below 100 °C. A detailed semiconductor-dielectric interface study has revealed that the high content of β-sheet structure in keratin protein has guided the P3HT polymer chains, through supramolecular forces of interaction to form 2D nanoribbons of large crystallite size (150 nm) over keratin thin film. This has led to the reduced trapping sites at the semiconductor/dielectric interface and hence the enhanced electrical performance of OTFTs was observed. Atomic force microscopy (AFM) and Grazing Incidence X-ray diffraction (GI-XRD) study was further employed to explore the mechanism of formation of 2D nanoribbons of P3HT. The primary and secondary structure of keratin protein as analyzed by AFM, Transmission electron microscopy (TEM) and Fourier transform spectroscopy (FTIR) is also provided in this study. The water compatible nature of keratin has helped to overcome the common issue of dielectric layer washing that occurs mostly during fabrication of OTFTs by sol-gel method. The biodegradable nature of keratin protein has also been demonstrated here by providing it as feed to fishes in an aquarium.

Cardanol-based polymeric gate dielectric for solution-processed organic field-effect transistors on flexible substrates

A cardanol-based polymer, poly(2-hydroxy-3-cardanylpropyl methacrylate) (PHCPM), was utilized as the gate dielectric of an organic field-effect transistor (OFET). PHCPM has good surface properties, appropriate gate dielectric characteristics, and good compatibility with solution-processed semiconducting polymers. The electrical properties of an FET that was prepared with natural resource-based PHCPM as a gate dielectric layer and solution-processed poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) as a semiconducting layer were investigated on flexible substrates. The flexible PBTTT-OFET device with the PCHPM gate dielectric exhibited high mobility and reliable performance, even in the bending state, without significant hysteresis.

Electrical properties of solution processed layers based on Ge-Si alloy nanoparticles

ABSTRACTGe-Si alloy nanoparticles (NPs) covering the full range of compositions were studied in regard to their suitability as semiconducting channel layer in thin-film transistors (TFTs). Special focus is given to the influence of annealing and encapsulation techniques on the contact and channel properties. Therefore, electrical characterization methods separating contact from channel characteristics are highlighted and applied. It is demonstrated that appropriate passivation of the nanoparticle surfaces can improve the Ion/Ioff ratios by modulation of the density of free charge carriers and also can suppress hysteresis effects. Ge-rich NP alloys can generally be passivated more effectively regardless if passivation is done with solution-processed poly(methyl methacrylate) (PMMA) or by aluminum oxide (Al2O3) from Atomic Layer Deposition (ALD). Sufficient annealing improves the contact formation between aluminum electrodes and Ge-Si particles by modification of charge injection. The presented analysis leads to a better understanding interface and surface effects in porous nanoparticle semiconductors for application in TFT devices.

(Poly(3,4-ethylenedioxythiophene):Polystyrene Sulfonate):Polytetrafluoroethylene for Use in High-Performance and Stable Bottom-Contact Organic Field-Effect Transistors

We successfully fabricated highly stable pentacene-based bottom-contact organic field-effect transistors (OFETs) with good charge injection properties at the electrode/organic semiconductor interface, obtained by optimizing the composition of solution-processed (poly(3,4-ethylenedioxythiophene):polystyrene sulfonate):polytetrafluoroethylene ((PEDOT:PSS):PTFE)-treated Au source/drain (S/D) electrodes. The (PEDOT:PSS):PTFE layer was deposited on the Au layer by spin-coating a mixture solution. The work function of the electrode increased from 4.84 to 5.21 eV as the PTFE concentration increased, accompanied by an interface dipole at the electrode surface. The optimized (PEDOT:PSS):PTFE (0.95:0.05)-treated electrodes significantly reduced the charge injection barrier at the electrode/semiconductor interface to achieve efficient charge transfer in the OFETs. Bottom-contact OFETs prepared with the optimized (PEDOT:PSS):PTFE-treated S/D electrodes had a field-effect mobility of 0.16 cm2/(V·s), which exceeded tha...

Poly(pyridinium iodide ionic liquid)-based electron injection layers for solution-processed organic light-emitting devices

Solution-processable poly(pyridinium iodide ionic liquid)-based electron-injection materials achieved more effective electron injection than the conventional Li-complex in OLEDs.

Solution-processed poly(3,4-ethylenedioxythiophene) nanocomposite paper electrodes for high-capacitance flexible supercapacitors

Nanostructured flexible PEDOT paper can be constructed by straightforward chemical polymerization on nanocellulose building blocks, yielding a high surface area, low sheet resistance and outstanding capacitive performance.

Thickness modulation effects of Al2O3 capping layers on device performance for the top-gate thin-film transistors using solution-processed poly(4-vinyl phenol)/Zn-Sn-O gate stacks

Solution-processed Zn-Sn-O (ZTO) top-gate thin-film transistors with Al2O3/poly(4-vinyl phenol) (PVP) double-layered gate insulators (GI) were fabricated and characterized. ZTO active channel was formed by spin-coating method and activated at a temperature as low as 350 °C. The chemical damages for the PVP films, which were induced during the photolithography-based patterning process were effectively suppressed by the introduction of Al2O3 capping layer. This capping layer also played an important role in improving the drain current hysteretic behaviors caused by intrinsic properties of the PVP film by modulating the capacitance coupling in the double-layered GI. The carrier mobility, subthreshold swing, and on/off ratio were obtained as approximately 5.13 cm2V−1s−1, 0.36 V/dec, 7.03 × 106, respectively, with hysteresis-free characteristics when the thickness values of Al2O3 capping and PVP GI layers were designed to be 90 and 220 nm, respectively.

Siloxane‐Based Hybrid Semiconducting Polymers Prepared by Fluoride‐Mediated Suzuki Polymerization

Siloxane-containing materials are a large and important class of organic-inorganic hybrids. In this report, a practical variation of the Suzuki polymerization to generate semiconducting polymeric hybrids based on siloxane units, which proceeds under essentially nonbasic conditions, is presented. This method generates solution-processable poly(diketopyrrolopyrrole-alt-benzothiadiazole) (PDPPBT-Si) consisting of the hybrid siloxane substituents, which could not be made using conventional methods. PDPPBT-Si exhibits excellent ambipolar transistor performance with well-balanced hole and electron FET mobilities. The siloxane-containing DPP-thiophene polymer classes (PDPP3T-Si and PDPP4T-Si), synthesized by this method, exhibit high hole mobility of up to 1.29 cm(2) V(-1) s(-1) . This synthetic approach should provide access to a variety of novel siloxane-containing conjugated semiconductor classes by using a variety of aryldihalides and aryldiboronic acids/esters.

Ultrathin ammonium heptamolybdate films as efficient room-temperature hole transport layers for organic solar cells.

Ammonium heptamolybdate (NH4)6Mo7O24·4H2O (AHM) and its peroxo derivatives are analyzed as solution-processed room temperature hole transport layer (HTL) in organic solar cells. Such AHM based HTLs are investigated in devices with three different types of active layers, i.e., solution-processed poly(3-hexylthiophene)/[6,6]-phenyl C61-butyric acid methyl ester(P3HT/PC60BM), poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]/[6,6]-phenyl C70-butyric acid methyl ester(PCDTBT/PC70BM) and evaporated small molecule chloro(subphthalocyaninato)boron(III) (SubPc)/C60. By virtue of their high work functions, AHM based HTLs outperform the commonly used poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) HTL for devices employing deep HOMO level active materials. Moreover, devices using AHM based HTLs can achieve higher short circuit current (Jsc) than the ones with evaporated molybdenum oxide(eMoO3), and thus better power conversion efficiency (PCE). In addition, P3HT/PC60BM devices with AHM based HTLs show air stability comparable to those with eMoO3, and much better than the ones with PEDOT:PSS.

Enhanced Performance of Polymer Solar Cells using PEDOT:PSS Doped with Fe3O4 Magnetic Nanoparticles Aligned by an External Magnetostatic Field as an Anode Buffer Layer

Low efficiency and poor stability are two major obstacles limiting the manufacturing of renewable and cost-effective polymer solar cell (PSCs). To address these problems, solution-processed poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) doped with Fe3O4 magnetic nanoparticles ((PEDOT:PSS):Fe3O4), and above (PEDOT:PSS):Fe3O4 thin film aligned by an external magnetostatic field ([(PEDOT:PSS):Fe3O4] W/H) were used as the anode buffer layer for PSCs, respectively. As compared with PSCs with PEDOT:PSS as an anode buffer layer, 38.5% enhanced efficiency and twice improved stability are observed from PSCs incorporated with [(PEDOT:PSS):Fe3O4] W/H anode buffer layer. It was found that enhanced efficiency and improved stability resulted from a combination of reduced acidity of PEDOT:PSS and enhanced electrical conductivity that originated from generated counterions and the paramagnetism of Fe3O4 magnetic nanoparticles by an external magnetostatic field.

Blending effect of 6,13-bis(triisopropylsilylethynyl) pentacene–graphene composite layers for flexible thin film transistors with a polymer gate dielectric

Solution processible poly(4-vinylphenol) is employed as a transistor dielectric material for low cost processing on flexible substrates at low temperatures. A 6,13-bis (triisopropylsilylethynyl) (TIPS) pentacene–graphene hybrid semiconductor is drop cast to fabricate bottom-gate and bottom-contact field-effect transistor devices on flexible and glass substrates under an ambient air environment. A few layers of graphene flakes increase the area in the conduction channel, and form bridge connections between the crystalline regions of the semiconductor layer which can change the surface morphology of TIPS pentacene films. The TIPS pentacene–graphene hybrid semiconductor-based organic thin film transistors (OTFTs) cross-linked with a poly(4-vinylphenol) gate dielectric exhibit an effective field-effect mobility of 0.076 cm2 V−1 s−1 and a threshold voltage of −0.7 V at V gs = −40 V. By contrast, typical TIPS pentacene shows four times lower mobility of 0.019 cm2 V−1 s−1 and a threshold voltage of 5 V. The graphene/TIPS pentacene hybrids presented in this paper can enhance the electrical characteristics of OTFTs due to their high crystallinity, uniform large-grain distribution, and effective reduction of crystal misorientation of the organic semiconductor layer, as confirmed by x-ray diffraction spectroscopy, atomic force microscopy, and optical microscopy studies.

Highly Efficient Polymer-Based Optoelectronic Devices Using PEDOT:PSS and a GO Composite Layer as a Hole Transport Layer

We demonstrate highly efficient polymer light-emitting diodes (PLEDs), as well as polymer solar cells (PSCs), using a solution-processable poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS):graphene oxide (GO) (PEDOT:GO) composite layer as hole transport layers (HTLs). The PEDOT:GO composite HTL layer shows enhanced charge carrier transport due to improved conductivity by benzoid-quinoid transitions with a well-matched work function between GO (4.89 eV) and PEDOT:PSS (4.95 eV). Moreover, it reduces remarkably exciton quenching and suppresses recombinations that bring higher charge extraction in PSCs and increases the recombinations of holes and electrons within the active layer by the blocking behavior of the electrons from a fluorescent semiconductor due to the existence of GO with large bandgap (∼3.6 eV) in the PEDOT:GO composite layer, therefore leading to an enhancement of device efficiency in PLEDs and PSCs. The optimized PLEDs and PSCs with a PEDOT:GO composite HTL layer shows the maximum luminous efficiency of 21.74 cd/A (at 6.4 V) for PLEDs, as well as the power conversion efficiency of 8.21% for PSCs, which were improved by ∼220 and 12%, respectively, compared to reference PLEDs and PSCs with a PEDOT:PSS layer.